Manifold sheet and process of making same



Dec. 22, 1953 J. G. ZIMMERMAN 6 MANIFOLD SHEET AND PROCESS OF MAKING SAME Filed March 17, 1948 INVENTOR. JEROME G. ZIMMERMAN nmwmm ATTORNEY Patented Dec. 22, 1953 MANIFOLD SHEET AND MAKING SAM West Milton, Ohio, asdard Register Jerome G. Zimmerman signor to The Stan PROCESS OF Company,

Dayton, Ohio, a corporationof Qhio Application' Marcl'r 17, 1948', Serial No. 15,501

8- Claims.

This invention relates to a manifolding whereby one or more copies of writing produced on an.

original sheet, for example by handwriting. or. typing, are reproduced on a copysheet or sheets placed beneath the Original sheet. Normally such copies are made by the transference of coloring, matter from a transfer coating, carried either onthe backs of the original or copy sheets, to an adjacent sheet or onto separate interleaved sheets.

It is an object of the present invention to provide a method of manifolding and the. means whereby the use of carbon black or other dark coloring matter transfer surfaces with their attendant disadvantages is dispensed with.

It is an object to provide a writing sheet of paper with a transfer surface on the rear which has thereon a solid, colorless, or substantially colorless coating containing a compound which is capable of reacting with hydrogen sulfide gas to. produce a dark or deep color. The coating must be capable of transfer to a contiguous paper surface at the points of impression upon the reverse side of the impacted sheet.

It is more particularly an. object to provide a writing sheet whose transfer surface on the rear has thereon a solid, colorless or light colored coating containing a water-soluble lead-, silver-,v stannous tin-, or bismuth-compoundcapable of reacting with hydrogen sulfide gas to produce a black or near black color and a water-soluble polyvalent metal salt of a certain type carboxylic acid; this coating must be capable of. transfer from the rear surface. of the sheet upon which the direct impression is made to the front surface of the contiguous sheet.

It is furthermorean object to provide a process of producing manifold sheets by treating the sheets with an emulsion which leaves thereon a firm coating upon drying of the components mentioned in the preceding paragraph.

Itis also an object to transfer from the transfer surface onto the copy sheet colorless or light colored characters which are the. duplicates of those formed upon the original sheet in a typing or writing operation, and then treat the copy sheet containing these colorless or substantially colorless characters with gaseous hydrogen. sulfide to create easily legible dark colored characters.

A further object of the invention is to provide av transfer surface or coating upon a sheet of writing paper having the advantageous features and inherent meritorious characteristicsv as hereinmentioned.

With the above primary and other incidental objects in view as will more fully appear in-the specification, the invention intended to be; protected by Letters Patent consists of the advantageous features, the components of the coating composition, and the mode of application and use as hereinafter described or illustrated in the accompanying drawing, or their equivalents.

In the accompanying drawing, which is of. a diagrammatic nature,

Fig. l is a view of a single. sheet: of writing; paper with the transfer coating applied. to the underside thereof, and

Fig. 2 is a view of an assembly of. superposed writing sheets forming a set of manifold record forms.

Like parts are indicated by similar characters. of reference throughout the several views.

According to the present invention the set of manifold materials comprises a seriesof two or. more sized sheets m, on. the rear surface of each sheet of the series (except the bottom sheet this is undesirable as explained below) there has been provided a substantially uniform, solid, colorless or very light colored coating l con taining a water-soluble metallic compound which is capable of reacting with hydrogen sulfide gas to produce a black, semi-black, or a brown color and a water-insoluble pol'yvalent metal salt of a higher fatty acid, naphthenic acid, or' a resin acid. Such water soluble metallic compounds are those of lead, silver, stannous tin and bismuth... This coating must be transferable from this rear surface at points of impact or pressure upon the. original sheet to the top surface of a contiguous paper surface to duplicate the imprinted characters. There is no reason actually for having the rear surface of the bottom sheet contain any coating unless an extra untreated sheet is inserted below it. The transfer letters, figures, etc. .are then caused to become legible by treating the copy sheets with hydrogen sulfide gas.

The explanation of the formation of the dark: colored, legible characters is that the hydrogen sulfide reacts with the colorless or light colored lead silver, stannous tin or bismuth compound in the transferred characters to form lead sulfides or the corresponding other metallic sulfides.

A suitable way to produce the coated transfersurface or surfaces ll of the sheet or sheets of this manifold system is to coat the rearsurface of every sheet (deducting one sheet if de sired, as the bottom sheet) with an emulsion made from a lead salt dissolved in water, a; waterinsoluble volatile. organic liquidv and; a. water-- insoluble polyvalent metal salt of a carboxylic acid selected from the group consisting of the higher fatty acids, naphthenic acid or resin acids, which latter salts are incapable of producing a black to brown color with hydrogen sulfide. The volatile water-immiscible organic liquid should be present in an amount exceeding the total weight of the other components mentioned which form the emulsion. Such an emulsion does not penetrate or wet the sized paper to any significant depth. When applied to the surfaces of sized sheets it dries to a thin film, which is not sticky or tacky. The finished coated surface possesses a fairly solid, uniform condition and is substantially dry.

Suitable organic liquids for the aforesaid emulsion are carbon tetrachloride, benzene, toluene, etc. They are inert with respect to the other components of this emulsion.

The water-insoluble polyvalent metal salt of the higher carboxylic acids may be those of aluminum, calcium or zinc. It is preferred to use aluminum stearate or the aluminum salts of other higher fatty acids; but the aforesaid metallic salts of naphthenic or the resin acids may be used. Water-soluble lead salts giving the best results are lead nitrate or the basic acetate. When the lead salts of the higher fatty acids are employed, such as lead palmitate, it is unnecessary to employ aluminum palmitate with lead nitrate or basic lead acetate. This is likewise true for the equivalents of each as set out previously.

Bleached shellac may be added to the emulsion to alter the color and improve the texture of the coating for some varieties of paper. The more bleached shellac present the lighter the color will be. But too much will hinder the reaction. Amounts of l-% are usually suitable. Instead of bleached shellac other light colored natural or synthetic resins which dry to a fairly solid state can be employed.

It has been found suitable to employ an emulsion to coat the sized paper made from a formula of the following type, each of which components must be of a light color:

Per cent by weight 1. Volatile organic liquid 77.5 2. Water-insoluble polyvalent metal salt (Al) other than lead, of a higher fatty acid 3.1 3. A water-soluble lead salt 3.9 4. Water 15.5

This emulsion, when applied to the back of sized paper and permitted to dry, yields sheets 10 coated on one surface with a substantially solid, uniform coating H which is not sticky or tacky.

For a fuller understanding of the nature and objects of the invention, reference should be had to the following examples which are given merely to illustrate the invention and are not to be construed in a limiting sense, all parts being given by weight:

Example 1 Per cent Carbon tetrachloride 77.5 Aluminum almitate 3.1 Lead nitrate 3.9 Water 15.5

The lead nitrate was first dissolved in water, whereupon these other ingredients were well mixed with this solution to form an emulsion. This was applied to the rear surface of the selected sized paper. The treated paper was then permitted to dry. The paper had a coating which was substantially white in color and solid to touch and was not sticky or tacky. A series of these forms was placed in a typewriter arranged with the coated surface at the rear of each sheet in the series; a plain, untreated sheet was below the last of the series. There was then typed out designated words and figures, the set of forms receiving the type blows from the typewriter, thus causing the light-colored coating to be transferred from the reverse side of the sheet at the point of percussion to the underneath sheets. The sheets, with the exception of the top sheet which carried the original, were then removed from the typewriter and exposed to dry hydrogen sulfide gas whereupon the previously practically invisible characters and figures became legible because of the chemical reaction. These were semi-black, clear, distinct and nonsmudging.

In the above example bleached shellac can be substituted u to 10% for the corresponding ratios of the other three components, carbon tetrachloride, aluminum palmitate and water. Methanol can be used to put it in solution.

Example 2 Per cent Carbon tetrachloride 77.5 Lead palmitate 6.9 Water 15.6

These three components were well mixed. The resulting emulsion was applied to the rear surface of the sized, selected sheets, and the other operations set out in the previous example carried out as there explained. The typed characters which were a dull black after the reaction with dry hydrogen sulfide gas were likewise clear, visible and substantially non-smudging.

It will be understood that, whereas certain specific examples have been described in the foregoing exposition of the invention, the present invention is not limited to these but is susceptible to various modifications and adaptations, as will be apparent to those skilled in the art, without departing from the scope of the invention as stated in the appended claims. In the claims the term colorless is used to embrace light colored shades as well as white. In both the specification and claims the term higher carboxylic acid or higher fatty acid denotes an acid of eight or more and preferably twelve or more carbon atoms. Where fatty acids are referred to there is meant those higher fatty acids present as glycerides in fatty oils and fats.

I claim:

1. A manifold sheet of sized paper on one side of which is a substantially uniform and solid, non-tacky, non-sticky, thin coating, which is colorless, containing as major components a water-soluble metallic compound selected from the group consisting of lead, silver, stannous tin and bismuth which compound is capable of reacting with hydrogen sulfide gas to produce a dark color, and a water-insoluble polyvalent metal salt of a carboxylic acid selected from the group consisting of the higher fatty acids, naphtheru'c acid and resin acids, which latter salt is incapable of reacting with this gas, the amount of these two metallic components being suflicient to provide a pressure transferable coating, the said coating being formed by the steps of claim 3.

2. A manifold sheet of sized paper on one side of which is a substantially uniform and solid.

non-tacky, non-sticky, thin coating, which is ture, water, a water-soluble lead compound and colorless, containing as major components a an aluminum salt of a carboxylic acid selected water-soluble lead compound and an aluminum from the grou consisting of higher fatty acids, salt of a carboxylic acid selected from the group p e e c ds a d resin d W c latter consisting of the higher fatty acids, naphthenic salt is incapable of producing a dark color with acid and resin acids, the amount of these two this gas, the Said Organ c olvent be P e metallic components being suflicient to provide n a am un by Weight exceeding that Of all a pressure transferable coating, the said coating the other components in the emulsitm, n being formed by the steps of claim 4. causing this coated sheet to dry, the amount of 3. In the process of producing a manifold sheet p s t d meta l mp nd be su i ent to comprising the steps of coating a surface of a provide a pressure transferable coating.

sized sheet of paper with a colorless emulsion The process Set 01113 in Claim 3, wherein a containingasubstantially inert water-immiscible light r d resin is p e t in t e emulsionorganic liquid which is volatile at room tem- A coated Sheet of sized paper Set out in perature, water, a water-soluble metallic comclaim pound selected from the group consisting of lead, The process'seif 01117 in claim wherein a Silver, Stannous tin and bismuth which light colored resin is present in the emulsion. pound is capable of reacting with hydrogen sul- A coated Sheet of slzed Paper set out in fide gas to produce a dark color, and a watercla'lm insoluble polyvalent metal salt of a carboxylic JEROME ZIMmRmN- acid selected from the group consisting of the higher fatty acids, naphthenic acid and resin References (med m the file of thls patent acdakwhilch lattizzgrt'ilalt is intclalpable of producing UNITED STATES PATENTS a ar co or wi is gas, e said organic solvent being present in an amount by weight exg g fi gf Au e1868 ceeding that of all the other components in the 1 355542 Decker 5 1920 emulsion, then causing this coated sheet to dry, 1633696 Davis 1927 the amount of deposited metallic compounds be- 7 Maier El 1930 ingt sufiicient to provide a pressure transferable 1'781902 Gm 1930 coa mg. i 30 4. In the process of producing a manifold sheet 33 as; 'hgi g comprising the steps of coating a surface of a 20832o6 ,schoeuer Jun'e 8'1937 sized sheet of paper with a colorless emulsion 2313810 Dalton 1943 containingasubstantially inert water-immiscible 2348123 Groak u 944 organic liquid which is volatile at room tempera- 35 ay 1 

3. IN THE PROCESS OF PRODUCING A MANIFOLD SHEET COMPRISING THE STEPS OF COATING A SURFACE OF A SIZED SHEET OF PAPER WITH A COLORLESS EMULSION COMTAINING A SUBSTANTIALLY INERT WATER-IMMISCIBLE ORGANIC LIQUID WHICH IS VOLATILE AT ROOM TEMPERATURE, WATER, A WATER-SOLUBLE METALLIC COMPOUND SELECTED FROM THE GROUP CONSISTING OF LEAD, SILVER, STANNOUS TIN AND BISMUTH WHICH COMPOUND IS CAPABLE OF REACTING WITH HYDROGEN SULFIDE GAS TO PRODUCE A DARK COLOR, AND A WATERINSOLUBLE POLYVALENT METAL SALT OF A CARBOXYLIC ACIDS, SELECTED FROM THE GROUP CONSISTING OF THE HIGHER FATTY ACIDS, NAPHTHENIC ACID AND RESIN ACIDS, WHICH LATTER SALT IS INCAPABLE OF PRODUCING A DARK COLOR WITH THIS GAS, THE SAID ORGANIC SOLVENT BEING PRESENT IN AN AMOUNT BY WEIGHT EXCEEDING THAT OF ALL THE OTHER COMPONENTS IN THE EMULSION, THEN CAUSING THIS COATED SHEET TO DRY, THE AMOUNT OF DEPOSITED METALLIC COMPOUNDS BEING SUFFICIENT TO PROVIDE A PRESSURE TRANSFERABLE COATING. 